Process of petroleum reduction



Patented Mar. 2,1920.

lvwentoz latter made UNITED STATES PATENT OFFICE.

FREDERICK A. KORMANN, OF NEW YORK, BROOKLYN,

N. Y., ASSIGNOR TO WILLIAM F. HULL, OF NEW YORK.

PROCESS OF PETROLEUM RED' UC'I'ION.

To all whom z't ma concerfn:

Be it known tiat I, Fnnnnmox A. Kon- MANN, a citizen of the United States, residing at New York city, in the oounty and State of New York, have invented certain new and useful Improvements in Processes of Petroleum Reduction; and I do hereby deolare the following to be a full, clear, and exact description of the same, reference being had to the accompanying drawings, forming part of this specification.

The invention relates to what is known as the alteration of a high boiling point hydrocarbon to a low boiling point hydrocarbon, and has no relation to that process com.- monly known as crackin The primary object of tlgie invention is to simplify the apparatus and the process of creating this physical change of a hydrocarbon oil, and thereby'greatly increasing the efliciency of output.

The further object of the invention is to produce a process that Will be without, periods of idleness in its operation and which will produoe a product Which is sweet in odor, clear in color, and does not become refractive when exposed to light.

The still further object of the invention is to produce an apparatus which shall be acoessible for alteration, and shall lrequire a minimum of time for interchange on cleaning, should such be necessary.

The further purpose of this invention is to procure from crude oil, kerosene, eto., a

ter volume of gasolene with a low b oiling point than has heretofore been possible to procure by any other process known to date.

Referrin part of this now to the drawings formng specifioation,--

Figure 1 re resents a diagrammatic view of a vprefer form of apparatusfor performlng my process.

Fig. 2 is a verticalv transverse sedsional view taken through the center of the retort to show the relative location of the pipes and the 'va'por chamber.

The operation is as follows: The'hyrocarbon, which may be gas oil, kerosene, erude oil, or in fact almost any liquid or solid hydrocarbon, or a oombination of either or both with a gaseous hydrocarbon, but is` prefera bly a liquid such as crude oil or kerosene, is placed in the' reservoir 1 and the Speciflcation of Letters Patent.

gas tight by closing the plug 2.

Patented Mar. 2, 1920.

1918. semu m. 245,331.

Steam is then admitted b in steam line 4 leading heated by any desired means, such as indicated by the numeral 6. I find it advisable to maintain a pressure of, say, 40 pounds per square inch, as indicated at 7, for treating an ordinary crude oil, and somewhat higher for the liquids heavier than 15 B aum. The steam thus passing through pipe 4 not only exerts pressure on the oil confined in the reservoir 1, but heats it as well and d-rives same through the pipe'7' to a spray 8 provided with graduated holes 9 for giving a fairly even Supply over the upper surface 10`of the porous or absorbent material 11 which closely fills the entire 4retort 12 except for the relatively small vapor chamber 13 between the surface 10 and the upper wall of the retort. Shortly before the oil is driven into the retort the burners 14 are lighted, subjecting the porous material to heat for the purpose of increasing the size of the minute orifices of the porous material' and also to drive out, or rather-to rarefy, the air therein occluded, thereby rendering the porous material in condition for maximum absorption. When the absorbent material is saturated or the receiver is emptied, as indicated by the gage glass 15, the valve 3 is closed, and the valve 16 in line 17 is opened, admltting steam to the superheater 18, the burner 19 of which is so regulated as to bring the temperature of the steam to a point about 100 F. above the end boiling point of the l-iquid being treated. A. lower temperature is possible 'but the above stated degree of heat has bn found in practiee to give :excellent results. The superheated steam passes through pipe 20 to a plurality of discharge pipes 21 provided with the usual graduated orifices to permit of uniform discharge of the superheated steam to alll parts of the absorbent.

I find it preferable to locate these pipes somewhat away from the vvalls of the retort 12 and to space them as far apart as they in turn `are spaoed from the walls, thereby imposing an even duty upon each P II has also been found advisable to locate the discharge holes 22 in the bottoms of the pipes directing the .steam downward, this to prevent as far as prcticalble the filling of thepipes 21 with oil and also-to lessen the work of clearing them when so filled.

rom the boiler 5 v It is preferable not to turn outI the burners 14; while drivin the treated oil from the absorbent materia the heat from these burners being advantageous, partly in keeping the steam at the desired temperature and partly in expand'mg the absorbent or porous material.

The superheated steam drives the oil from its confinement up through the wbsorbent material to the vapor dome 13, and from thenoe to the vapor line 23 leading therefrom to a wndenser coil 24 of any preferred type. The com'bined vapors are here condensed to a liquid which ma be withdrawn through cock 25 to a retainer 26, this retainer in practice being a regulation oil tank havin the usual accessories for discharge of t e finished product, etc. The cock 25 is normall open so that no back pressure is exerteil against the saturated steam, but it is closed when pressure is transmitted to the reservoir and retort during the first part of the process, z". e., while the absorbent material is being saturated.

Although the water and oil vapors mix in line 23, no difliculty is thereby encountered as the water sinks to the bottom of the tank 26 and is withdrawn from the system at that point. In` the use of the process as now practiced, the indications are that the a'bsor ent material may clog u after'a considera'ble. period of use at W ich time it should be cleaned or renewed, but I do find, however, that practically the entire volume of li uid put into the system is received therefrom in the form of gasolene from cock 25, or in a heavy liquor which is drained from the retort 12 by cock 27, the retort being placed at a slight angle to the horizontal for the purpose of easy drainage of this refuse liquor, the amount of such residiial liquor varying from 0 for kerosene to ne-arl 90 per cent. for some of the lower grade exican type crude oils from which not over one or two per cent. o solene can be obtained b the usual me rods.

I may make one or oth heads of the retort readily re'movable for convenience in replacing the wbsorbent material and the various pipes, or may .provide manholes for this purpose, 'but since all these are well known in the art, they are not illustrated in the drawin and may readily be desi ed for the desired use by any mechanic skilled in the art.

The porous element materially contracts when saturated, probably due to the driving out of a great part of the occluded air by the heat and the sealing of the holes by the incoming relatively cool' oil. In 'any event it is true that bricks of absorbent material when saturated with oil are considerably smaller in volume and are somewhat darker in color than a normal brick, and that when a saturate brick is subjected to heat and the confined oil iven ofl', it returns to its normal size and oo or and the same is true when a brick is left exposed to a current of air.

It is my belief that the contracton of the 'absorbent material after saturation has a material influence on the change of the physioal properties of the confined oil, possibly by the exertion of reat ressure in the sa e manner as the p ysica properties of bits of charcoal are totally altered by immersion in molten iron, followed by the chilling1 of the iron mass.

By t is theory the oil entering one of the minute orifices of the porous material or a'bsorbent mass, naturally Causes a contraction first of all at the mouth of the cavity. The mouth of the orifioe thus starts to contract before the oil reaches the further end of the cavity, and continues to contract until the mouth of the hole or pore is entirely closed, causing the formation of a closed cavity filled with the oil, Which cavity, by the same law of oontraction, continues to oontract thereby exerting upon the minute quantity of oil therein contained a pressure running up to a very considerable degree. This is true to a still greater extent When the absorbent material is hot and the oil entering the pores is relative] ool.

t may be, however t at the absorbent material II use is merel an inert catalytic agent-bearing in min however, that the relatively great contraction of the absorbent material, while saturated, is not a theorj7 but is a physical fact-and ermits of the alteration of the hydrocarbon molecules when finely divided, in the same manner as the chloroform when passed through platinum black in the presence of hydrogen changes to formalin.

I have stated in the three preceding paragraphs my present theories of the reasons or the operation of the process, but do not positively claim accuraey for them, and do not wish to be limited thereby, my invention consistingI in the lowering of the boiling point of a relatively heavy carbon compound by the action of an absorbent or porous material, irrespective of whether that material acts as a catalyzer or as a contracti'ng medium, or both.

To substantiate the theory of the physical change without the cheinical alteration, Ihave proven that by using a high boilin point hydrocarbon, with an end point o 650 F., and sirbjectin same to treatment as above stated, the tota volume on condensation hasv an end int of not to exceed {fm F., and is still o the same series of hydrooarbon products.

process is adaptable to either the crude oil of petroleum, or'the disti'llates thereof, and is continuous of operation.

The material used as the absorbing agent' nasamo is preferably composed of shale clay, or a composition of shale clay, bone and Willow charcoal, so combined as to be in the form of a solid mass by intermingling in the presence of moisture, and then compressed and dried and finally burned to produce a porous brick. I do the use of shale clay and charcoal solely, but I am embodying as absorbent those elements, pr their vegetable, mineral or animal equivaents.

As an example of the merits of this process, I will give the data of a crude oil known as Kentucky crude of 33 Baum gravity, treated under this process. The retort was charged to its maximum capacity of abso tion with this above mentioned oil, and t e distillation was carried to a oint at which 95 per cent. of the origina volume used was converted into a gasolene body of approximately 50 Baum, with an end point of 440 F., the usual yield being 33 er cent.

With Blackwell (Oklahoma) cru e of 41 Baum, the retort was charged to its maximum capacity of absorption, and the distillation was carried to a point at which 90 per cent. of the original volume used was converted into a gasolene body of approximately 52 Baum, with an end point of 404 F., the usual yield being 32 per cent.

With Texas coastal crude of 21.5 gravity, the retort Was charged to its maximum capacity of absorption, and the distillation was carried to a point at Which 34 per cent. of the original volume usedv Was converted into a gasolene body of approximately 50 Baum, with an end point of 431 F., show,- ing a yield of 340 per cent. of that produced by the best present practice.

From a exican crude oil of 12 Baum gravity, we obtained under this process, 16 per cent. of gasolene, with an end point of 450 F., the usual yield of this type being 2 per cent. or less, my process, therefore, showmg an eight-fold yield over the best results now obtainable.

A similar demonstration of the process Was carried out With a kerosene, with an end point of 600 F., 44.5 Baum gravity, the distillation carried to a point of exhaustion of the original charge, and the product had a gravity of 52 Baum, With an end point of 450 F.

In thus treating kerosene by my process there is no more loss than is usual in the ordinary distillation of a good grade gasole'ne. and vet I secure a reduction of 150 F. in the boiling point of the liquid.

While I have described my process in its preferred form in great detail, I wish it distinctly understood that what I have developed is the broad invention of reducing hydrocarbon in the manner stated and desire to cover all minor changes and unpatentably different methods such as the shutting not limit the invention to off of burners 14 during the process or the use of compressed air in pipe 4, for example, the use of which was discontinued When the advantages of the use of steam were understood.

What is claimed is: 4

1. The process of altering the physical properties of a hydrocarbon by absorbing said hydrocarbon into the interstices of a heated absorbent material and in then driving said hydrocarbon from said absorbent material by the application of heat Without destroying said absorbent material in said process.

2. The process of expandin a ca illary tube by heat, delivering a cooer hy rocarbon thereto, thus contractin said ca illary tube, and in driving out the ydrocar on in the form of a vapor by the application of further heat.

3. In a cyclic process of obtaining gasolene from a heavler hydrocarbon, the steps of subjecting a porous material to heat, filling the ores of such material While so heated with a li uid hydrocarbon thus cooling said materia reheating said porous material thereby driving the hydrocarbon from said pores in the form of a vapor thus lacin such porous material in condition or a re lling of its pores With hydrocarbon.

4. In the rocess of obtaining asolene from a relatlvely steps of fillin the pores of a orous material compose in part of a clarigying agent With a liquid hydrocarbon heavier than gasolene thereby reducing the total volume of said material, and subjecting the material and the therein confined hydrocarbon to suflicient heat to vaporize the hydrocarbon content as a clarifiedasolene.

5. In the process of o taining gasolene from a relatlvely heavier hydrocarbon, the conversion ste s which consist in c'ausin the absorption o a li uid hydrocarbon y :l porous substance an applying heated steam to said substance so as to drive out the resulting hydrocarbon.

6. The process of obtaining a gasolene froma heavier hydrocarbon which consists in the cycle of beating a porous material to a temperature of about five hundred degrees Fahrenheit, delivering the hydrocarbon thereto whereby said porous material is cooled and a portion of the hydrocarbon is volatilized, reheating the porous material lu'radually to about five hundred degrees Fahrenheit thereby volatilizing the greater portion of said hydrocarbon and raismg the porous material to the temperature necessary to continue the process by4 the delivery of a further quantity oi hydrocarbon and in ccndensng the gasolene vapors so produce FREDERICK A. KORMANN.

heavier hydrocar on, the 

